EP1385928B1 - Procede de purification d'alkylphenols a longue chaine et produits d'addition de mannich desdits alkylphenols - Google Patents

Procede de purification d'alkylphenols a longue chaine et produits d'addition de mannich desdits alkylphenols Download PDF

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Publication number
EP1385928B1
EP1385928B1 EP02764066A EP02764066A EP1385928B1 EP 1385928 B1 EP1385928 B1 EP 1385928B1 EP 02764066 A EP02764066 A EP 02764066A EP 02764066 A EP02764066 A EP 02764066A EP 1385928 B1 EP1385928 B1 EP 1385928B1
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EP
European Patent Office
Prior art keywords
phenol derivative
phase
extracting agent
process according
polyisobutenylphenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP02764066A
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German (de)
English (en)
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EP1385928A1 (fr
Inventor
Arno Lange
Hans Peter Rath
Marc Walter
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/16—Reaction products obtained by Mannich reactions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases

Definitions

  • the present invention relates to a process for the purification of polyisobutenylphenols having a number average molecular weight of 200 to 4000 and Mannich adducts thereof.
  • Aminoalkylated polyalkylenephenols as obtainable by Mannich reaction of amines and aldehydes with polyalkylene-substituted phenols, play an important role as fuel additives for keeping valves and carburetors or injection systems of gasoline engines clean (cf., for example, BM Rossenbeck in Catalysts, Surfactants, US Pat. Mineral oil additives, ed. J. Falbe, U. Hasserodt, S. 223, G. Thieme Verlag, Stuttgart 1978).
  • the crude reaction products of the Mannich reaction often exhibit varying detergency and are associated with a number of disadvantages. Due to the complex composition of the mixtures is often observed a dark color and an intense odor, which adversely affect customer acceptance. In many cases, the viscosity at low temperatures is too high, which can lead to the so-called valve plugging. This refers to the complete loss of compression on one or more cylinders of the internal combustion engine when the spring forces are no longer sufficient to close the valves properly.
  • the cause of the undesirable properties are often by-products and low molecular weight fractions resulting from the preparation of the alkylphenol.
  • the alkylphenols used as starting material are usually prepared by alkylation of phenol with polyolefins, such as polyisobutene. In the alkylation with polyisobutene is often a decrease in the molecular weight, d. H. a partial cleavage of the polyisobutene chain observed.
  • the cleaved isobutene may form lower alkylphenols, such as tert-butylphenol or tert-octylphenol.
  • US 3,368,972 describes a motor oil additive composition containing Mannich adducts of alkyl-substituted hydroxyaromatic compounds. Suitable hydroxyaromatic compounds include polypropylphenol, polybutylphenol and polyamylphenol.
  • the reaction mixture is treated with dimethylamine and formaldehyde to remove unreacted amine and formaldehyde with toluene and butyl alcohol and washed three times with hot water.
  • Example 2 of this document describes the preparation of a polybutylphenol from phenol and polybutene in the presence of BF 3 phenolate as catalyst. For workup, the reaction mixture is treated with methanol and ammonia and stirred with heating. The resulting organic phase is washed again with methanol.
  • the present invention has for its object to provide a simple method for the removal of by-products and low molecular weight fractions of long-chain alkylphenols and their Mannich adducts.
  • this object is achieved by a process for the purification of a phenol derivative selected from polyisobutenylphenols having a number average molecular weight of 200 to 4000 or Mannich adducts thereof, comprising the phenol derivative with an extraction agent having a polarity E T (30) of 57 to 38 kcal / mol, preferably 56 to 48 kcal / mol, intimately bringing into contact, a phenol derivative-containing phase and an extractant phase can be separated from each other and the extractant phase is removed.
  • a polarity E T (30) of 57 to 38 kcal / mol, preferably 56 to 48 kcal / mol
  • a polyisobutenylphenol can be subjected to the process according to the invention; the purified polyisobutenylphenol can then be converted to a Mannich adduct, as described below.
  • a crude polyisobutenylphenol can be subjected to the process according to the invention; the purified polyisobutenylphenol can then be converted to a Mannich adduct, as described below.
  • the phenol derivative can be subjected as such, ie in substance, the process of the invention.
  • a non-polar solvent ie one having a polarity E T (30) of 35 to 30 kcal / mol
  • the nonpolar solvent and the relative amount of the nonpolar solvent relative to the phenol derivative are chosen so that at the temperature at which the process of the invention is carried out, the solution of the phenol derivative and the extractant are not completely miscible. In other words, they have a miscibility gap, so that spontaneous separation into a phenol derivative-containing polar phase and an extractant phase takes place after contacting.
  • Suitable non-polar solvents are aliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, n-octane and their isomers, petroleum ether, ligroin, benzene, toluenes, xylenes or commercial solvent mixtures, such as Solvesso® or Aromatics® 150, as well as mixtures thereof.
  • the solution generally has a content of phenol derivative of at least 5 wt .-%, usually 20 to 90 wt .-%.
  • the extractant used is a solvent having a polarity E.sub.T (30) of 57 to 38 kcal / mol, preferably 56 to 48 kcal / mol.
  • E.sub.T polarity of 57 to 38 kcal / mol, preferably 56 to 48 kcal / mol.
  • the determination of the solvent polarity on the E T (30) scale is described in Liebigs Ann. Chem. 1983, 721-743, to which reference is made in full. It has been found that solvents of the indicated polarity have a high solubility for the by-products and low molecular weight fractions, but are immiscible with the phenol derivative so that they form a separate phase in which the by-products and low molecular weight fractions accumulate and are easily removed can.
  • the polarity of the extractant is lower than indicated, it does not show satisfactory phase separation with the phenol derivative. If the polarity is higher than indicated, the dissolving power of the extractant is insufficient
  • the extractant phase or the phenol derivative-containing phase is the heavier phase.
  • the separating extractant phase is generally recognizable by the intense dark coloration that results from the extracted colored by-products.
  • Extractants suitable for the process according to the invention are, above all, the substance classes of the alcohols, such as methanol, ethanol, n-propanol or isopropanol, nitriles, such as acetonitrile, ketones, such as acetone or butanone, or esters, such as ethyl acetate, or butyl acetate, lactones, such as butyrolactone To assign amides, such as formamide or dimethylformamide.
  • Preferred extractants are methanol, ethanol, n-propanol, isopropanol, acetone or butanone.
  • mixtures of the solvents with one another or with water are suitable, for. B. in an amount of up to 20 wt .-%.
  • a suitable extractant is z.
  • the contacting can be carried out continuously or discontinuously.
  • Several discontinuous operations may be carried out in cascade, with the phenol derivative-containing phase separated from the extractant phase each being contacted with a fresh portion of extractant.
  • discontinuous implementation brings under mechanical movement, for. By stirring or shaking, the phenol derivative or its solution in a non-polar solvent and the extractant in a suitable vessel, the mixture is allowed to rest for phase separation and one of the phases is removed by conveniently drawing off the heavier phase at the bottom of the vessel.
  • the extractant is preferably passed to the phenol derivative in an extraction zone.
  • advantageously used vertically arranged separation columns which are usually provided to provide a high phase exchange surface with packing or moving or stationary fixtures.
  • the heavy phase is preferably fed in the upper region of the separation column, the lighter phase in the lower region of the separation column and thus countered each other.
  • the light phase settles at the head of the separation column on the heavy and can be removed through an overflow pipe.
  • the heavy phase collects at the bottom of the separation column and can be removed, preferably via a riser.
  • the phenol derivative-containing phase may be divided and the extractant phase may be undivided or vice versa.
  • the success of the purification process according to the invention can be monitored, in particular in the case of continuous or cascade-like performance, by determining the concentration of the extracted constituents in the spent extractant. This can be done by measuring density or refractive index. Likewise, methods of IR or UV-VIS spectroscopy, optionally in an "on-line" method, are used. You can the cleaning method z. B. cancel if the concentration has fallen below a predetermined value.
  • the spent extractant can be worked up, e.g. B. by distillation or membrane processes. In this case, it can be separated into unreacted starting materials, such as phenols, which can be recycled to the production process, and by-products which are discarded.
  • the inventive method is a depletion of by-products and low molecular weight fractions in Phenolderivat by a factor of more than 10, in particular more than 20, easily possible.
  • the inventive method is generally carried out at a temperature of 0 to 120 ° C, preferably 10 to 60 ° C, z. At room temperature. It generally works at normal pressure, with working at overpressure is also possible.
  • Polyisobutenylphenols which can be purified by the process of the invention are generally obtained by reacting a phenol with a substantially monounsaturated olefin of suitable chain length in the presence of an alkylation catalyst.
  • phenol (unsubstituted) phenol itself or substituted phenols are suitable.
  • the substituted phenols preferably have, in addition to the hydroxyl group, one or two further substituents, which are preferably in the ortho position to the hydroxyl group.
  • Suitable substituents are, for. B. C 1 -C 4 alkyl or C 1 -C 4 alkoxy. Particularly preferred are phenol, 2-methylphenol and 2-ethylphenol.
  • polyisobutenes in particular so-called “highly reactive polyisobutenes, having a proportion of isobutene units of more than 80 mol%, in particular more than 90 mol%, are used.”
  • the polyisobutenes preferably have a number-average molecular weight in the range from 500 to 1500 and a polydispersity between 1.1 and 5.0, preferably less than 1.9, polydispersity is the quotient of the weight-average molecular weight M w by the number-average molecular weight M n .
  • the alkylation is suitably carried out at a temperature of -10 to 80 ° C, preferably 0 to 40 ° C.
  • Suitable alkylation catalysts are protic acids such as sulfuric acid, phosphoric acid and organic sulfonic acids, e.g. B. trifluoromethanesulfonic acid; Lewis acids such as aluminum trihalides, e.g. For example, aluminum trichloride or aluminum tribromide, boron trihalides, z. As boron trifluoride and boron trichloride, tin halides, z. Tin tetrachloride, titanium halides, e.g.
  • Lewis acid alkylation catalysts can be used in combination with electron donors such as alcohols, especially C 1 -C 6 alkanols, phenols or ethers. Particularly preferred are boron trifluoride etherate and boron trifluoride phenolate.
  • Suitable solvents for the alkylation are hydrocarbons, in particular aliphatic hydrocarbons such as pentane, hexane and heptane, petroleum benzines with boiling ranges between 35 and 100 ° C, dialkyl ethers, eg. As diethyl ether, and halogenated hydrocarbons, such as dichloromethane or trichloromethane. Likewise, aromatics, such as toluene, xylene, and their isomers can be used.
  • hydrocarbons in particular aliphatic hydrocarbons such as pentane, hexane and heptane, petroleum benzines with boiling ranges between 35 and 100 ° C
  • dialkyl ethers eg. As diethyl ether
  • halogenated hydrocarbons such as dichloromethane or trichloromethane.
  • aromatics such as toluene, xylene, and their isomers can be used.
  • the alkylphenol is reacted with an aldehyde and a primary or secondary amine. Suitable methods are for. In US-A 4,231,759; US-A 4,117,011; US-A 5,634,951; US-A 5,725,612; GB 1,368,532 or the older applications DE 199 48 114.8 and DE 199 48 111.3.
  • formaldehyde is preferably reacted.
  • Suitable formaldehyde sources are aqueous formaldehyde solution and formaldehyde oligomers such as trioxane and paraformaldehyde.
  • Suitable primary amines are methylamine, ethylamine, n-propylamine, isopropylamine, dimethylaminopropylamine, aniline and benzylamine.
  • Suitable secondary amines are dimethylamine, diethylamine, piperidine, morpholine and piperazine.
  • the reaction products of alkylene oxides, in particular ethylene oxide are suitable with primary amines.
  • the water of reaction formed in the Mannich reaction can be removed by heating in the presence of an entraining agent.
  • Suitable entrainers are benzene, toluene, xylene and mixtures thereof.
  • Alkylphenol, aldehyde and amine are preferably used in a molar ratio of 1: 0.5: 0.5 to 1: 4: 4.
  • polyisobutenylphenols and their Mannich adducts can be purified by the process of the invention, it is particularly suitable for 4-polyisobutenylphenol and its Mannich adducts.
  • the Mannich adduct purified by the process according to the invention or a Mannich adduct prepared from a phenol derivative purified by the process according to the invention is suitable as a surfactant or surface-active substance, eg. B. as a detergent additive in fuel and lubricant compositions, optionally in combination with other conventional fuel and lubricant additives.
  • additional components are polyalkene mono- or polyalkene polyamines, nitropolyisobutanes, hydroxynitropolyisobutanes, copolymers of C 2 -C 40 -olefins with maleic anhydride whose carboxyl groups are completely or partially neutralized, sulfosuccinic acid alkyl esters and salts thereof, tridecanol or isotridecanol butoxylates, isononylphenol butoxylates, adipates, Phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, polypropylene oxide and polybutylene oxide, and derivatives thereof.
  • the xylene was removed by evaporation (without prior washing with methanol).
  • 100 g of the Mannich base were stirred for 30 minutes with 100 ml of methanol.
  • the product phase was separated off and residual amounts of methanol were removed on a rotary evaporator at 100 ° C. and 20 mbar. There was obtained 94 g of purified product.
  • the methanol phases were distilled off on a 100 cm long packed column with stainless steel wire mesh coils, the following fractions were obtained: 1400 g of methanol (64 ° C to 68 ° C, 950 mbar); 105 g of phenol (69 ° C to 72 ° C, 12 mbar); and 5 g of BF 3 -methanol complex (76 ° C to 80 ° C, 12 mbar).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (8)

  1. Procédé de purification d'un dérivé de phénol choisi parmi des polyisobuténylphénols ayant un poids moléculaire moyen numérique de 200 à 4000 ou des produits d'addition de Mannich de ceux-ci, dans lequel on met intimement en contact le dérivé de phénol avec un agent d'extraction d'une polarité ET(30) de 57 à 38 kcal/mole, on laisse se séparer l'une de l'autre une phase contenant du dérivé de phénol et une phase à agent d'extraction et on élimine la phase à agent d'extraction.
  2. Procédé suivant la revendication 1, dans lequel l'agent d'extraction présente une polarité ET(30) de 56 à 48 kcal/mole.
  3. Procédé suivant la revendication 1 ou 2, dans lequel on dissout le dérivé de phénol dans un solvant ayant une polarité ET(30) de 35 à 30 kcal/mole et on met en contact la solution avec l'agent d'extraction.
  4. Procédé suivant l'une des revendications 1 à 3, dans lequel l'agent d'extraction est choisi parmi du méthanol, de l'éthanol, du n-propanol, de l'isopropanol, de l'acétone, de la butanone ou leurs mélanges ou leurs mélanges avec de l'eau.
  5. Procédé suivant l'une des revendications précédentes, dans lequel le polyisobuténylphénol présente un poids moléculaire moyen numérique de 500 à 1500.
  6. Procédé suivant l'une des revendications précédentes, dans lequel le produit d'addition de Mannich est le produit de la réaction du polyisobuténylphénol avec du formaldéhyde et une amine primaire ou secondaire.
  7. Procédé suivant l'une des revendications précédentes, dans lequel, pour ce qui concerne le polyisobuténylphénol, il s'agit d'un 4-polyisobuténylphénol.
  8. Procédé suivant l'une des revendications précédentes, dans lequel l'agent d'extraction passe à contre-courant du dérivé de phénol dans une zone d'extraction.
EP02764066A 2001-04-23 2002-04-22 Procede de purification d'alkylphenols a longue chaine et produits d'addition de mannich desdits alkylphenols Expired - Lifetime EP1385928B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10119738A DE10119738A1 (de) 2001-04-23 2001-04-23 Verfahren zur Reinigung von langkettigen Alkylphenolen und Mannich-Addukten davon
DE10119738 2001-04-23
PCT/EP2002/004415 WO2002086037A1 (fr) 2001-04-23 2002-04-22 Procede de purification d'alkylphenols a longue chaine et produits d'addition de mannich desdits alkylphenols

Publications (2)

Publication Number Publication Date
EP1385928A1 EP1385928A1 (fr) 2004-02-04
EP1385928B1 true EP1385928B1 (fr) 2006-01-25

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EP02764066A Expired - Lifetime EP1385928B1 (fr) 2001-04-23 2002-04-22 Procede de purification d'alkylphenols a longue chaine et produits d'addition de mannich desdits alkylphenols

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Country Link
US (1) US7355082B2 (fr)
EP (1) EP1385928B1 (fr)
AT (1) ATE316566T1 (fr)
DE (2) DE10119738A1 (fr)
WO (1) WO2002086037A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101892098A (zh) * 2010-07-22 2010-11-24 山西新源煤化燃料有限公司 一种低碳含氧组分油及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3368972A (en) * 1965-01-06 1968-02-13 Mobil Oil Corp High molecular weight mannich bases as engine oil additives
US3904595A (en) 1973-09-14 1975-09-09 Ethyl Corp Lubricating oil dispersant
US4101590A (en) * 1976-08-23 1978-07-18 Maruzen Oil Co., Ltd. Process for separation and purification of vinylphenol
NL7712270A (en) * 1977-11-08 1979-05-10 Sterlitamaxky O Promyshlenny Methyl-di:tert.-butyl:phenol purification - by crystallisation from aq. methanol at low temp.

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Publication number Publication date
US20040133048A1 (en) 2004-07-08
DE50205709D1 (de) 2006-04-13
WO2002086037A1 (fr) 2002-10-31
EP1385928A1 (fr) 2004-02-04
US7355082B2 (en) 2008-04-08
DE10119738A1 (de) 2002-10-24
ATE316566T1 (de) 2006-02-15

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